Starch-fluoro polymer textile sizing,water and oil repellent composition

ABSTRACT

A TEXTILE SIZING, I.E., STARCHING WHICH ALSO IMPARTS A MEASURE OF WATER AND/OR OIL-REPELLENCY CONTAINING A WATER-SOLUBLE STACH AND A FLUOROPOLYMER EMULSION DISPERSED, PREFERABLY, UNDER THE AEGIS OF NORMALLY GASEOUS PROPELLANT.

United States Patent 3,813,359 STARCH-FLUORO POLYMER TEXTILE SIZING,WATER AND OIL REPELLENT COMPOSITION Robert Tweedy Hunter, Jn, Mendham,and Herman Lowell Marder, Plainfield, N.J., assignors to Colgate-Palmolive Company, New York, N.Y.

No Drawing. Continuation of abandoned application Ser. No. 740,437, June19, 1968. This application Feb. 4, 1972, Ser. No. 223,735

Int. Cl. C08d 9/06 US. Cl. 260-174 ST 6 Claims ABSTRACT OF THEDISCLOSURE A textile sizing, i.e., starching, composition which alsoimparts a measure of Water and/or oil-repellency containing awater-soluble starch and a fluoropolymer emulsion dispersed, preferably,under the aegis of normally gaseous propellant.

This is a continuation, of application Ser. No. 740,437, filed June 19,1968, and now abandoned.

The present invention relates to a new and outstanding textile treatingcomposition and particularly to compositions of the type normally usedpreparatory to ironing textiles. The compositions serve primarily tosize and impart waterand oil-repellency. By sizing is meant the abilityto stiffen the textile and in many instances to add gloss to the textilesurface.

The use of starch as a size and stiffening agent for textile materialsis probably as old as textile themselves. It is only within the lastseveral decades that the housewife has been offered such a product in analready prepared liquid form for application to the textile beforeironing. Such starching compositions are now available in a variety offorms and among the most popular is an aerosol-type formulation.

It is well known that in order to obtain a desirable stiffening of thetextile material after washing, it is necessary after each washing andbefore each ironing to treat the textile with the starching composition.Obviously, this is so because of the non-durable nature of the sizingcompositions used. As a practical matter, it is necessary that thesizing, i.e., starching composition, be non-durable and produce nobuild-up of stiffening action from one wash to another since this wouldlead to stiffening of the textile material to an undesirable degree inmost instances. By virture of the non-durable characteristics of theconventional starching compositions, it is possible for the housewife tocontrol the degree of size and stiffening with each product at any giventime.

It is also known to treat textile materials with various waterand/ oroil-repellent compositions, and usually such operations are carried outin the mill during the manufacture of the base textile material althoughit is not by any means uncommon to find products which can be used forsuch purposes by the housewife and which are in fact so used on anindividual basis to produce a water repellent or an oil repellent finishon the textile material. The products normally employed for producingwater repellency and/or oil repellency do not produce any stiffening orsizing action on the textile. However, such compositions which have infact combined a starch formulation with an oil and/ or water repellencyproducing material has resulted in a formulation with strong durabilitycharacteristics for the oil and water repellency portion of theformulation. Clearly, a build-up of such a material will produceundersirable features.

The present invention provides a sizing or stiffening composition, i.e.,a starch composition, which not only produces the desired degree of sizeand stiffness, which not only aifords control by the consumer of thesecharacteristics by virtue of the non-durability between washings of thisfinish, but also provides Water and oil repellency which is non-durablein nature.

The compositions of the present invention comprise as the essentialingredients thereof, a Water soluble or water dispersible sizingmaterial, which is a polysaccharide as exemplified by the variousnatural starches and the various starch derivatives such as oxidizedstarches, acylated starches, starch ether, hydrolyzed starches,enzyme-treated starches and the like. The starch composition is incombination with a thermoplastic film-forming fluorocarbon polymer ashereinafter described. In addition to the starch and fluoro polymerthere may also be present in the compositions of this invention manyother additives which do not adversely affect the attainment ofnon-durable stiffening along with non-durable water and oil repellency.Examples of such additional materials include anti-stick agents such asthe siloxane resins, polyethylene and the like; additional waterrepellent materials such as long chain fatty quaternary ammoniumcompounds; anti-oxidants; anti-foamers; stabilizers; bacteriacides;surface active agents; coloring materials; perfumes; textilefiber-reactive chemicals, e.g., formaldehyde, glyoxal; crease resistantand crease proofing agents, and the like.

The preferred form of the compositions of this invention is aself-propelling liquid composition wherein the major carrier liquid iswater and the propellant is a suitable low boiling hydrocarbon orhalogenated hydrocarbon as exemplified by methylchloride,methylenechloride, isobutane and the various chlorinated fluorinatedmethanes, ethanes, and the like, such as dichlorodifluoro methaneand thelike.

The non-durable size or stiffening component is preferably selected fromthe general class of starches and starch derivatives and among these themost preferred material is an acetylated amylopectin which is a thinboiling cookup type starch and is illustrative of the preferred class ofproducts of high fluidity, i.e., 30 to (intrinsic viscosity of from 1.0to 0.3). Other starch products which may be employed include thefollowing: gelatinized rice starch, gelatinized tapioca ethoxylatedstarch, gelatinized carboxymethyl starch, nitrogenated starch, oxidizedcorn starch, alkylated starch, dextrins and the like.

The amount of starch material which may be employed in the compositionsof this invention may be varied widely, but in general from about 1% toabout 10% thereof based on the total weight of the aerosol formulationmay be used. More important than the specific amount of size material,is the ratio of the latter to the fluorocarbon polymer employed. Ingeneral, the ratio of these two components may vary from about 1:2 to100:1 (size to fiuoro polymer) and within this range it is preferred toemploy a ratio of from about 2:1 to 20:1. By the use of theaforementioned ratios and, particularly, the narrower range, it has beenfound that an outstanding non-durable stiffening action is obtainedwhich does not interfere with the provision of excellent repellentcharacteristics.

The fiuoropolymer component of the compositions of this inventioncomprise a thermoplastic polymeric material having a molecular weight ofless than 3 0,000 in the form of an emulsion, known as a latex, which ischaracterized by the ability to dry to a continuous cohesive film.Fluoro polymers are well known but those which are preferred frommonomers in the present invention comprise the general class of theperfluoro acrylates and alpha-substituted acrylates, such asmethacrylates, all having in common the fact that they are of a lowmolecular weight. Such fluoro polymers are prepared from thecorresponding monomers but include a chain transfer agent, e.g.,alkanethiol, such as dodecyl mercaptan, to terminate the polymer. Asillustrative of the fluoro polymers which maybe used in the presentinvention, mention may be made of the following:

Homipolymers of:

lH,lH-perfluorohexyl acrylate 1H,lH-perfluorocetyl acrylatel-H,lH-perfluorodecyi acrylate 1H,lH-perfiuorododecyl acrylate lI-I,lH-perfluorohexyl methacrylate 1H,1H-perfluorodecyl methacrylatelH,1H-perfluorododecyl methacrylate 1H,1H-perfiuorohexyl-wfiuoroacrylate1H,1H-perfluorodecyl-a-fluoroacrylate l H,1H,7H-penfiuoroheptyl acrylate1H, 1H, 1 lH-perfluoroundecyl methacrylate lH,lH,1 lH-perfluoroctylacrylate 1H,lH,3H-perfluoroocetyl-wfluoroacrylate1H,lH-perflnoroheptyl-a-chloroacrylate the general formula of which maybe presented as follows:

wherein X is hydrogen, chlorine or fluorine; X is hydrogen, alkyl (C toC chlorine or fluorine, n has a value of 3 to 30, m=l, 2 or 3. X ishydrogen, lower alkyl (C to C or halogen and at least 70% but not lessthan 6 of the Xs are fluorine; interpolymers (i.e., copolymers andterpolymers of the aforementioned monomers; with poly merizable vinylcompounds, said interpolymer containing at least 25 mole percent offluoro monomer.

Suitable comonomers include:

vinyl esters of organic and inorganic acids, e.g., vinyl chloride; vinylbromide; vinyl fluoride; vinyl acetate; vinyl propronate; vinylstearate; vinyl benzoate;

vinyl ethers, e.g., methyl vinyl ether; ethyl vinyl ether; n-butyl vinylether; decylvinyl ether; octadecyl vinyl ether; benzyl vinyl ether;phenyl vinyl ether; and divinyl ether;

alkyl vinyl ketones (alkyl C to C alkyl acrylates (alkyl C to C alkylmethacrylates (alkyl C to C vinyiidene halides acrylic acidacrylonitrile acrylamide N-methylol acryiamide; N-methoxy methylacrylamide styrene, alkyl styrenes 1,3-butadiene alkyl esters alkylhalides monoand di-acrylate esters of alkanediols monoand di-vinylesters of alkanedieic acids and the like.

It is of primary importance to the practice of the invention to achievenon-durability of the fiuoro polymer by utilizing a low molecular weightfiuoro polymer latex which dries by itself to a brittle film,

Other resin emulsions may be added to the compositions of this inventionto give special benefits. Thus, one may add minor amounts (up to about300% of the weight of fiuoro polymer) based on the weight of the totalcomposition of any of the aforementioned fluorinated polymers amongothers, e.g., acrylic emulsions, such as Rhoplex 13-15, polyl,3-dichlorobutadiene, polysiloxane emulsions, polyethylene emulsions,polybutadiene emulsions, polystyrene emulsions, and the like.

A typical low molecular weight fiuoro polymer product is prepared fromthe following: (polymerization run at 70 C. for 5 hours).

2 parts n-butyl acrylate 2 parts octadecyl dimethylamine acetate 1.2parts dodecyl mercaptan 200 parts water The polymer produced by thistechnique is of much lower molecular weight than that normally preparedin the absence of the chain transfer agent, namely, dodecyl mercaptan.

The formulations of the present invention may be used in any convenientconcentration in a bath spray, roller padder or aerosol method ofapplication. Generally concentrations are selected to give a solidpick-up based on the material treated of between 0.1 to 10% by weight.Since in order to obtain uniform treatment of a textile, it is desirableto have from about 1% to 200% and preferably from about 25 to wetpick-up the concentrations of active components in the treatingcomposition for the preferred pick up will vary from about 40% down to0.1%. Clearly, such concentrations are not critical and are subject tothe wide variation and great latitude indicated above.

In the preferred and most convenient method of application by theconsumer of the composition of this invention, i.e., aerosol method, theaqueous compositions are formulated with a suitable propellant. Theseinclude trichloromonofluoromethane, dichlorotetrafiuoroethane,dichloromonofluoromethane, monochlorotrifluoromethane, rochloroethaue,1,1,l-cyclobutane, car-bondioxide, nitrous oxide.

In general the propellants are Water-immiscible or only slightly solublein water with vapor pressures at 70 F. of from about 0.2 to about 500p.s./g. The selection of a suitable propellant or mixture of propellantswill, of course, depend on the type of package to be used, the specificnature of the composition to be dispensed, and the spray patterndesired, among others. Where lower pressures are to be maintained in thepackage it ma be desirable to use a propellant of slight watersolubility to aid in dispensing the product after it leaves the nozzle.

The preferred propellants are the low density compounds and mixtures oflow density which form a separate and upper liquid phase in the aerosolpackage providing thereby a separate phase system. While it is notintended to foreclose the use of higher density propellants (i.e.,higher than the aqueous latex phase) in which case the propellant willbe on the bottom in the aerosol package, this is not preferred becauseof the inadequacies of the mechanics of the package required fordispensing such compositions and further because other means for makingsuch systems workable (i.e., shortened dip tube) create undesirableeconomic factors (e.g., cannot discharge a high percent of the activeingredients). In order to achieve the benefits of this invention,however, any technique aerosol or otherwise may be employednotwithstanding the fact that the optimum results may be obtained withcertain specific formulations and techniques and these might, ingeneral, be preferred especially by the housewife.

The amount of propellant as well as the specific one or ones used willvary depending upon the pressure limitations on the package and thespray pattern desired. Generally from 3% to 25% by Weight of propellantcircumscribes the practical range thereof, and as pointed out above,among these the low density, medium vapor pressure hydrocarbons such asisobutane are preferred.

As previousl pointed out many other adiuvants may be used in thecompositions of this invention, some with particularly noteworthyresults. Thus incorporation of a polyethylene emulsion or poly1,3-dichlorobutadiene emulsion in amounts ranging from to 300% by weightbased on the weight of fluoropolymer gives rise to unique ironingcharacteristics to textiles sprayed with such modifiedembodiments aswill be seen hereinafter.

The following examples serve to illustrate the present invention withoutbeing deemed limitative thereof. Parts are by weight unlessot'herwiseindicated.

EXAMPLE. I

A composition is prepared of the following components: 27% a'c'etylatedamylope'c'tin (thin boiling starch characterized by a viscosity of 14.4cps. or a 5% solution in water measured at 76 F., pH=5.2) 0.3% copolymerproduced from the following:

(a) 1H,1H,2H,2H tridecafiuorooctyl methacrylate (97% (b) n-butylacrylate (2%) (c) dodecyl mercaptan (1%) Balance water A sample ofcotton fabric is immersed in the above aqueous composition squeezed to50% pick-up, air dried until slightly damp and ironed at 400 F. todryness. The resultant fabric exhibits good waterand oil-repellency andhas a crisp handle characteristic of a starched material.

EXAMPLE H 20 parts acetylated amylopectin (National 1135 starch) 1 partchain terminated copolymer as a 25% solids latex as produced at (A)above.

The resultant was compounded to produce an aqueous formulation of 10%starch, 5% fluoro polymer, 7% isobutane as the propellant.

EXAMPLES III TO VII In these examples a basic starch containingpreparation is prepared by cooking 3.2 grams of National Starch CompanysNo. 1135 in approximately 500 grams of deionized water for approximatelminutes. The solution was allowed to cool to room temperature and 1 gramof 37% formaldehyde solution was added, for preservative purposes, andthe entire batch was diluted with cool, deionized water to a finalweight of 640 grams.

80 gram portions of this starch concentrate were used in formulation ofaerosol preparations in accordance with these examples. The final weightof each formulation was 150 grams. The propellant was isobutane so thatit comprised 7% isobutane. The formulations had various additivesincorporated therewith as set forth below wherein the starch isequivalent to 2.6% starch solids in the final formulation and the otheringredients are as indicated:

TABLE I Percent Fluoro Example Starch polymer Non-fiuorinated polymer 2.67 0.3 0.6 acrylic emulsion. 2.67 0.3 0.6 poly 1,3-dichlorobutadieneemulsion.

2.67 0.3 0.6 polyethylene emulsion. g. 0.3

Example VIII is considered a control so that in the following testmethod the tested swatches were not treated.

The fluoro polymer in the above was of the low molecular weight typeproduced in accordance with A in the above.

The acrylic emulsion used in Example III is further identified asRhoplex B-15, a product of Rohm and Haas Co.

The aerosol preparations of Examples III to VII are used in the uniformspraying to wetness of white cotton 6. swatches having an x 80 count sothat there is a 50% wet pick up. The swatches are heat cured in aconventional manner as by ironing at 400 F. at a rate of about 33seconds/foot to dryness.

Several tests can be employed to establish the effectiveness of thepresent process for imparting water repellent and oil repellentproperties to the various substrates employing the formulations producedin Examples III to VII.

While a number of tests have been devised to determine the degree ofstain resistance of fabrics and the subsequent launderability thereof,many of the tests fail by reason of the difliculty of making such testsconsistently reproducible. Colgate-Palmolive research scientists havedeveloped an ingenious test system which overcomes the shortcomings ofthe previous tests. Essentially, their method consists of placing ontothe fabric measured volumes of standard common staining materials andcomparing the size and intensity to a visual standard. In this way asemi-quantitative estimation of the staining characteristics of a givenfabric is obtained.

The test technique employs three water borne stains, namely, (1)chocolate milk, (2) black coffee, and (3) imitation Coke; and three oilborne stains, namely, (4) flue dyed corn oil, (5) French dressing, and(6) blue dyed petroleum oil.

The staining materials mentioned in the above have the followingcompositions:

1. Chocolate milk stain This stain should be prepared once a week andkept refrigerated.

2. Black coffee G. Instant coffee 1.5 Boiling water 98.5

The coffee solution is allowed to cool until it reaches 70*- 80 F. Thestain should not be kept for more than eight hours.

3. Imitation Coke Cc. Coke syrup 50 Isopropanol 50 Water 4. Blue dyedcorn oil 0.40 g. blue dye is added to 400 g. corn oil with stirring andheat in order to obtain a uniform solution.

5. French dressing Once a bottle is opened, it should be stored in arefrigerator.

6. Blue dyed petroleum oil 250 g. of oil are mixed with 0.1% blue dye byweight of the oil. The mixture is agitated and warmed in order to obtaina uniform solution.

The test in the instant case is a static stain repellency test in thatthe fabric surface is given a minimum disturbance.

In application the temperature of the stain materials is between 70-80F. A piece of white fabric approximately 7 inches by 7 inches is placedon blotting paper on a hard surface. 1% cc. of each test stain iscarefully placed (not dropped) in separate areas on the fabric. Aftertwo minutes, the excess stain material, if any, is removed using avacuum suction line without coming in physical contact with the stainedsurface. The stained area is brushed twice lightly in oppositedirections with a straight motion of a dry absorbent tissue to removeany unabsorbed stain material.

The stains are rated against the white background of a clean blotter.Ratings of 1 through 5 are arrived at strictly on size (relative spread)of an individual stain while rating 6 through 10 determines relativewetting as measured by intensity of the stain against a standard.

In other words, a stain not even wetting the fabric could not change thecolor of the fabric and would have been completely removed from thesurface thereof. The rating, therefore, would be 10. With increasingwetting of the area to which the stain has been applied there would be agreater color intensity therefore a lower rating until 6 is reached,whereupon, if the stain has migrated from its original boundary then onecan assume complete wetting of the original area so that degree ofmigration becomes the determining factor. The greater the migration, thelower the number given. It will be appreciated that the test system isbased on relative values, and yet provides unique reproducible validresults.

The three water borne stains are added together to give a possiblemaximum of 30. Likewise the oil borne stains are added to give a maximumpossibility of 30. These may then be totalled for a maximum of 60.

To arrive at the launderability portion of the test, the stained fabricsare dried 24 hours. Laundering is then carried out by washing in anautomatic washer with a quantity of a conventional detergent. Thefabrics are then dried in an automatic dryer at the appropriate settingfor the fabric type. They are then lightly dry ironed (stain side down)at the appropriate fabric setting.

The rating of launderability of stains is based on the same 1-10 systemused for the static stain repellency tests. Again, it will be noted thatthe maximum rating after adding the results of the water borne stainswill be 30, and similiarly 30 will be the total results regarding theoil borne stains. These two may be added together.

By rating both the initial static stain repellency and thelaunderability, a complete picture can be obtained not possible whenonly the initial stain reaction is determined.

COLGJKTE-PALMOLIVE TEST I Initial static staining RepollencyLaunderability Ex. W.B. 0.13. Total V7.8. 0.3. Total l Water bornestain. I Oil borne stain.

Aesthetic qualities,

Examples ease of ironing III Good. IV Very good. V 'Do. VI Fair. VIIPoor.

By carrying out replicates of the swatches treated by the formulationsof Examples III to VII as before, but subjecting all of them to a singlewash with a detergent in a conventional washing cycle followed by dryingand ironing, durability results are obtained as follows:

Repellency Launderability Ex. W13. 0.13. Total W.B. 0.3. Total When onecompares the results of Test II with Test I it will be noted that thestain repellency isalmost completely eliminated and compares with theresults of Example VIII or Test I. i

EXAMPLE IX Example 11 is repeated wherein the propellant and amountthereof is varied as follows (with a corresponding change in percentwater):

Example I is repeated using the following water-soluble carbohydrates inthe indicated amounts. Where more or less than 2.7% is used, there is'acorresponding change in the water present:

Percent A. Thin boiling wheat starch-fluidity 87 2.0 B. Thin boilingwheat starch-Aiuidity 87 l.. 5.2 C. Thin boiling wheat starch-#fluidity98 8.2 D. Modified cornstarch-fluidity 60 3.1 E. Modifiedcornstareh-fluidity 75 6.2 F. Sulfated amylopectin (18 oz. starch) 7.0G. Oxyethylated starch-fluidity 65 2.8

The results are comparable to Example I.

EXAMPLE XI Example I is against repeated except that the fiuoro polymeramount is as follows:

A. 0.14% B. 0.03% C. 1.4% D. 0.6% E. 0.15%

ple I.

As the above examples illustrate, the compositions of I this inventionproduce excellent sizing along with unique waterand oil-repellency ontextiles. The compositions may be applied to the textiles in anyconvenient manner although they are most superior when used in anaerosol form. Where the propellant in these compositions is more densethan the aqueous components, the package structure will, obviously, varyfrom those packages or containerused with propellants which are lessdense than and form an upper discrete liquid phase. Regardless of thesevariations, however, excellent. properties are forthcoming in allinstances.

Many substances maybe added to the compositions of I this invention, aspointed out above, and-as will be 0b..

vious to one skilled in the art, the parameters are ex- The results areequivalent to those obtained in Exam tremely varied, particularly inview of the fact that none of the additives need be soluble either inwater or the selected propellant. Where it is desired, a compound may beadded as a solution in a suitable solvent and such solution added to theaqueous compositions producing in most instances a dispersion of thesaid compound in the compositions. Many other variations will beapparent and it is clear that these may be resorted to without departingfrom the spirit and scope of this invention and that the specificembodiments set out herein are in no way limitative thereof.

What is claimed is:

1. A containerized, non-durable, aqueous aerosol textile treatingcomposition for sizing and rendering a textile oil and water repellentconsisting of,

(A) a major amount of Water-immiscible propellant mixture, and

(B) a minor amount of a component mixture of,

(1) a water soluble starch characterized by a fluidity value of 30 to100, and

(2) a thermoplastic fiuoro polymer of an alkyl acrylate containing 1-30C in the alkyl group and at least 2.5 mole percent of a polymerizablecompound of the formula wherein X is selected from the group consistingof hydrogen, C to C alkyl, chlorine and fluorine: X is selected from thegroup consisting of hydrogen, chlorine and fluorine, and X is selectedfrom the group consisting of hydrogen, C to C alkyl and halogen: n has avalue of 3 to 30: m has a value of 1 to 3; and at least 70%, but atleast 6 of the Xs are fluorine and said thermoplastic fiuoro polymerhaving a molecular weight of less than 30,000, said components (1) and(2) being present in the range of 1:2 to 100:1.

2. A composition as defined in claim 1 wherein the polymer contains from1 to mole percent of a C to C alkyl acrylate in polymerized form.

3. A composition as defined in claim 2 wherein the polymer contains from1 to 10 mole percent of a C to C alkyl acrylate.

4. A composition as defined in claim 3 wherein the polymer contains from1 to 10 mole percent N-methylol acrylamide.

5. A composition as defined in claim 4 wherein the formula of thepolymerizable compound (B)(2) is 6. A composition as defined in claim 1wherein the, starch is acetylated amylopectin.

References Cited UNITED STATES PATENTS 3,575,899 4/1971 Pryor et al260-174 2,461,139 2/1949 Caldwell 260-234 3,347,812 10/1967 De Marco etal. 260--29.6 3,356,628 12/1967 Smith et al 260-29.6 3,068,187 12/1962Bolstad et a1. 26029.6 3,503,915 3/1970 Peterson 260-29.2 3,532,65910/1970 Hager 26029.6 3,592,686 7/1971 Barber 117--161 OTHER REFERENCESR. W. Kerr, Chemistry and Industry of Starch, 2d ed., Academic Press(1950), pp. 582-585.

WILLIAM H. SHORT, Primary Examiner E. WOODBERRY, Assistant Examiner US.Cl. X.R. 117139.5 C, A

